CN102206175A - Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature - Google Patents
Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature Download PDFInfo
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- CN102206175A CN102206175A CN2011100966992A CN201110096699A CN102206175A CN 102206175 A CN102206175 A CN 102206175A CN 2011100966992 A CN2011100966992 A CN 2011100966992A CN 201110096699 A CN201110096699 A CN 201110096699A CN 102206175 A CN102206175 A CN 102206175A
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- 239000002253 acid Substances 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 30
- HAOGQMYNUDFRPS-UHFFFAOYSA-L [N+](=O)([O-])C=1C(=C(C(C(=O)[O-])=CC1)O)[N+](=O)[O-].[Na+].[Na+].[N+](=O)([O-])C=1C(=C(C(C(=O)[O-])=CC1)O)[N+](=O)[O-] Chemical compound [N+](=O)([O-])C=1C(=C(C(C(=O)[O-])=CC1)O)[N+](=O)[O-].[Na+].[Na+].[N+](=O)([O-])C=1C(=C(C(C(=O)[O-])=CC1)O)[N+](=O)[O-] HAOGQMYNUDFRPS-UHFFFAOYSA-L 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- TYWAOIBYSDORAH-UHFFFAOYSA-N 1,2-bis(4-aminophenyl)ethane-1,2-dione Chemical compound C1=CC(N)=CC=C1C(=O)C(=O)C1=CC=C(N)C=C1 TYWAOIBYSDORAH-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 azo compound Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid, in particular to a method for preparing the DSD acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature. The method comprises the following steps of: (1) dissolving a raw material DNS (DiNitroSalicylic) acid; (2) adding a catalyst and materials into a hydrogenating reactor for carrying out hydrogenation; (3) filtering the catalyst; (4) precipitating with acid; and (5) carrying out filter pressing by virtue of a plate frame. The invention is innovative in that the method for preparing the DSD acid by hydrogenating and reducing the disodium dinitrosalicylate is developed. High-concentration disodium dinitrosalicylate is adopted to prepare the DSD acid, thus space-time capacity of equipment is improved, and one-time investment of the equipment is reduced; and a high temperature continuous feeding way is adopted for reaction, thus the reaction is carried out toward the direction more beneficial to a main reaction, a side reaction is effectively controlled, generation of coloured impurity can be effectively controlled, and quality and yield of the DSD acid are greatly improved.
Description
Technical field
The present invention relates to a kind of method of the DSD of preparation acid, especially a kind of high temperature hydrogenation reducing DNS acid disodium salt prepares the method for DSD acid.
Background technology
4,4 '-diaminobenzil 2,2 '-disulfonic acid (DSD acid) and disodium salt thereof are the important intermediate of preparation toluylene type white dyes, Qi Shi substantive dyestuff and reactive dyestuffs.The substantive dyestuff of being made by DSD acid, does not have in human body and accumulates and be subjected to extensive attention because nontoxicity with the various active dyestuff.
At present, the production technique of DSD acid mainly adopts the method for preparing DSD acid by iron powder reducing DNS sodium salt.Patent documentation CN1785970A discloses a kind of method of preparing DSD acid by iron powder reducing DNS sodium salt, and this procedure comprises: under violent stirring, add sodium-acetate, formic acid or sodium formiate and the vitriol oil as additive in the reactor that iron powder and water are housed.After the iron powder pre-etching, add the DNS sodium salt solution under 95-100 ℃ and violent stirring condition, control pH value is at 5.1-5.6.After 95-100 ℃ of insulation, adjust the pH value to 9-11 with the whole derivation of reaction solution and to wherein adding NaOH solution, remove by filter iron mud, to filtering back gained filtrate adding sulphuric acid soln adjustment pH value, filter once more and obtain DSD acid to 1-2.This complex technical process, energy consumption height, wastewater flow rate is big, and a large amount of dangerous solid waste iron mud that produces causes severe contamination to environment.According to the requirement of scientific development, country is to the environmental requirement increasingly stringent, and iron powder reducing technology is progressively eliminated, thereby exploitation is cleaned, the catalytic hydrogenating reduction technology of less energy-consumption, and is imperative.
For DSD acid hydrogenation technique, document (Chen Hongbo etc., fine chemistry industry, 2003,6,374) use water as reaction medium, Pd/C is a catalyzer, has studied liquid phase catalytic hydrogenation method reduction 4,4 '-dinitrobenzene toluylene 2,2 '-disulfonic acid (DNS) preparation 4,4 '-diaminobenzil 2,2 '-disulfonic acid (DSD acid).By a series of condition experiments, definite optimum process condition is: raw material DSD acid disodium salt 10g; Mass concentration is 180g/L; Pd/C catalyzer 0.8g; Promotor OVN80mg; Reaction system pH=6; 65 ℃ of temperature of reaction; Pressure 0 8MPa.But there is following weak point in this technology: the one, and yield is low; The 2nd, temperature of reaction is low, and speed of reaction is slow, generates azo compound easily, and products obtained therefrom purity is low, causes cotton thread dyeing index defective; The 3rd, the concentration of the DNS acid disodium salt that adopts is low, and equipment capacity is restricted, and improve throughput, must strengthen facility investment.Therefore, do not see the industrialized report of DSD acid hydrogenation technique so far.
Summary of the invention
Technical problem to be solved by this invention provides to be had environmental protection, less energy-consumption, is easy to realize that a kind of high temperature hydrogenation reducing DNS acid disodium salt of advantages such as industrialization prepares the method for DSD acid.
Method of the present invention comprises the steps:
(1) add solid DNS acid disodium salt in dissolution kettle, adding water adjusting DNS acid disodium salt mass concentration is 40-70%, opens and stirs, and is warmed up to 120 ℃ the DNS acid disodium salt is fully dissolved;
(2) catalyzer is added in the catalytic hydrogenation reaction device, add the water of reactor volume 15%, after being replaced into nitrogen atmosphere in the reactor, feed hydrogen, keep pressure 0.5-3.0Mp;
(3) open hydrogenator and stir, be warming up to 250-300 ℃, the DNS acid disodium salt solution in the dissolution kettle was squeezed in the hydrogenator continuously with the time of 1-2h reacted, after charging finishes, continue to keep above-mentioned reaction conditions 20min;
(4) react the process filter that finishes and filter out catalyzer, reclaim to give over to and applies mechanically, material enters in the acid out still;
(5) open the acid out still and stir, the adding mass concentration is 50% sulphuric acid soln, and acid out to pH value is 1-2, obtains DSD acid suspension liquid;
(6) DSD acid suspension liquid is squeezed into the plate-and-frame filter press press filtration behind the acid out, gets finished product DSD acid.
In the step (1), preferred DNS acid disodium salt mass concentration is 50-60%.
In the step (2), preferred reaction pressure is 0.8-1.8Mpa; Preferred temperature of reaction is 260-280 ℃.
In the step (2), the add-on of described catalyzer is the 0.5-5% of DNS acid disodium salt quality.
In the step (2), described catalyzer is palladium carbon, platinum carbon or ruthenium carbon.The metal quality mark is 0.5-10% in the catalyzer, and the metal quality mark is 1-3% in the preferred catalyzer.
The invention has the advantages that:
1. owing to adopt hydrogen reducing to replace iron powder reducing, avoid producing the severe contamination that a large amount of dangerous solid waste iron mud causes environment;
2. adopt high density DNS acid disodium salt to prepare DSD acid, improved speed of reaction greatly, saved the reaction times.
3. adopt high density DNS acid disodium salt to prepare DSD acid, improved the space-time production capacity of equipment, reduced the one-time investment of equipment;
4. the mode of continuously feeding is reacted under the employing high temperature, and reaction is carried out towards the direction that more helps main reaction, has effectively controlled side reaction, thereby can control the generation of foreign pigment effectively, improve the yield and the purity of DSD acid, the yield of DSD acid can reach more than 99%, and purity is more than 98.5.
5. solved DSD acid hydrogenation technique and be difficult to an industrialized difficult problem, its enforcement will produce remarkable economic efficiency, environmental benefit and social benefit.
Embodiment
Embodiment 1
In the stirring-type still of 1000L, add entry 400L, solid DNS acid disodium salt 400kg opens and stirs, and is warming up to 120 ℃ the DNS acid disodium salt is fully dissolved.
Adding metal quality mark is 3% platinum C catalyst 12kg in the 1000L hydrogenator, adds entry 150L, is replaced into nitrogen atmosphere, feeds hydrogen, keeps pressure 1.8MPa.The unlatching reactor stirs, and is warming up to 250 ℃, with 1h the DNS acid disodium salt solution in the dissolution kettle is squeezed in the hydrogenator with the fresh feed pump continuously and smoothly and is reacted.After charging finishes, continue to keep above-mentioned reaction conditions 20min.
With hydrogen emptying in the reactor and be replaced into nitrogen atmosphere, filter out catalyzer through high-performance filter, catalyst recovery gives over to applies mechanically, and material enters in the acid out still.Opening the acid out still and stir, is that 50% sulphuric acid soln acid out to pH value is 2 with mass concentration, obtains DSD acid suspension liquid.
DSD in acid out still acid suspension liquid is got the wet product 502kg of DSD acid after the plate-and-frame filter press press filtration.
Product is 99.8% with the DNS acid disodium salt rate of collecting, DSD acid HPLC content 98.5%.
Embodiment 2
In the stirring-type still of 1000L, add entry 150L, solid DNS acid disodium salt 350kg opens and stirs, and is warming up to 120 ℃ the DNS acid disodium salt is fully dissolved.
Adding metal quality mark is 1% palladium-carbon catalyst 3.5kg in the 1000L hydrogenator, adds entry 150L, is replaced into nitrogen atmosphere, feeds hydrogen, keeps pressure 0.8MPa.The unlatching reactor stirs, and is warming up to 300 ℃, with 1.5h the DNS acid disodium salt solution in the dissolution kettle is squeezed in the hydrogenator with the fresh feed pump continuously and smoothly and is reacted.After charging finishes, continue to keep above-mentioned reaction conditions 20min.
With hydrogen emptying in the reactor and be replaced into nitrogen atmosphere, filter out catalyzer through high-performance filter, catalyst recovery gives over to applies mechanically, and material enters in the acid out still.Opening the acid out still and stir, is that 50% sulphuric acid soln acid out to pH value is 1 with mass concentration, obtains DSD acid suspension liquid.
DSD in acid out still acid suspension liquid is got the wet product 426.9kg of DSD acid after the plate-and-frame filter press press filtration.
Product is 99.5% with the DNS acid disodium salt rate of collecting, DSD acid HPLC content 98.8%.
Embodiment 3
In the stirring-type still of 1000L, add entry 200L, solid DNS acid disodium salt 300kg opens and stirs, and is warming up to 120 ℃ the DNS acid disodium salt is fully dissolved.
Adding metal quality mark is 10% palladium-carbon catalyst 1.5kg in the hydrogenator of 1000L, adds entry 150L, is replaced into nitrogen atmosphere, feeds hydrogen, keeps pressure 3MPa.The unlatching reactor stirs, and is warming up to 260 ℃, with 2h the DNS acid disodium salt solution in the dissolution kettle is squeezed in the hydrogenator with the fresh feed pump continuously and smoothly and is reacted.After charging finishes, continue to keep above-mentioned reaction conditions 20min.
With hydrogen emptying in the reactor and be replaced into nitrogen atmosphere, filter out catalyzer through high-performance filter, catalyst recovery gives over to applies mechanically, and material enters in the acid out still.Opening the acid out still and stir, is that 50% sulphuric acid soln acid out to pH value is 2 with mass concentration, obtains DSD acid suspension liquid.
DSD in acid out still acid suspension liquid is got the wet product 357.3kg of DSD acid after the plate-and-frame filter press press filtration.
Product is 99.6% with the DNS acid disodium salt rate of collecting, DSD acid HPLC content 99.1%.
Embodiment 4
In the stirring-type still of 1000L, add entry 450L, solid DNS acid disodium salt 300kg opens and stirs, and is warming up to 120 ℃ the DNS acid disodium salt is fully dissolved.
Adding metal quality mark is 0.5% ruthenium C catalyst 15kg in the 1000L hydrogenator, adds entry 150L, is replaced into nitrogen atmosphere, feeds hydrogen, keeps pressure 0.5MPa.The unlatching reactor stirs, and is warming up to 280 ℃, with 1h the DNS acid disodium salt solution in the dissolution kettle is squeezed in the hydrogenator with the fresh feed pump continuously and smoothly and is reacted.After charging finishes, continue to keep above-mentioned reaction conditions 20min.
With hydrogen emptying in the reactor and be replaced into nitrogen atmosphere, filter out catalyzer through high-performance filter, catalyst recovery gives over to applies mechanically, and material enters in the acid out still.Opening the acid out still and stir, is that 50% sulphuric acid soln acid out to pH value is 1 with mass concentration, obtains DSD acid suspension liquid.
DSD in acid out still acid suspension liquid is got the wet product 383.2kg of DSD acid after the plate-and-frame filter press press filtration.
Product is 99.5% with the DNS acid disodium salt rate of collecting, DSD acid HPLC content 98.6%.
Embodiment 5
In the stirring-type still of 1000L, add entry 350L, solid DNS acid disodium salt 350kg opens and stirs, and is warming up to 120 ℃ the DNS acid disodium salt is fully dissolved.
Adding metal quality mark is 2% ruthenium C catalyst 10.5kg in the 1000L hydrogenator, adds entry 150L, is replaced into nitrogen atmosphere, feeds hydrogen, keeps pressure 1.0MPa.The unlatching reactor stirs, and is warming up to 270 ℃, with 1h the DNS acid disodium salt solution in the dissolution kettle is squeezed in the hydrogenator with the fresh feed pump continuously and smoothly and is reacted.After charging finishes, continue to keep above-mentioned reaction conditions 20min.
With hydrogen emptying in the reactor and be replaced into nitrogen atmosphere, filter out catalyzer through high-performance filter, catalyst recovery gives over to applies mechanically, and material enters in the acid out still.Opening the acid out still and stir, is that 50% sulphuric acid soln acid out to pH value is 1 with mass concentration, obtains DSD acid suspension liquid.
DSD in acid out still acid suspension liquid is got the wet product 447.1kg of DSD acid after the plate-and-frame filter press press filtration.
Product is 99.5% with the DNS acid disodium salt rate of collecting, DSD acid HPLC content 98.7%.
Embodiment 6
In the stirring-type still of 1000L, add entry 450L, solid DNS acid disodium salt 300kg opens and stirs, and is warming up to 120 ℃ the DNS acid disodium salt is fully dissolved.
Adding metal quality mark is 5% palladium-carbon catalyst 6kg in the 1000L hydrogenator, adds entry 150L, is replaced into nitrogen atmosphere, feeds hydrogen, keeps pressure 2.0MPa.The unlatching reactor stirs, and is warming up to 290 ℃, with 1.5h the DNS acid disodium salt solution in the dissolution kettle is squeezed in the hydrogenator with the fresh feed pump continuously and smoothly and is reacted.After charging finishes, continue to keep above-mentioned reaction conditions 20min.
With hydrogen emptying in the reactor and be replaced into nitrogen atmosphere, filter out catalyzer through high-performance filter, catalyst recovery gives over to applies mechanically, and material enters in the acid out still.Opening the acid out still and stir, is that 50% sulphuric acid soln acid out to pH value is 1 with mass concentration, obtains DSD acid suspension liquid.
DSD in acid out still acid suspension liquid is got the wet product 383.2kg of DSD acid after the plate-and-frame filter press press filtration.
Product is 99.5% with the DNS acid disodium salt rate of collecting, DSD acid HPLC content 98.6%.
Claims (8)
1. a high temperature hydrogenation reduction high concentrate DNS acid disodium salt prepares the method for DSD acid, it is characterized in that comprising the steps:
(1) add solid DNS acid disodium salt in dissolution kettle, adding water adjusting DNS acid disodium salt mass concentration is 40-70%, opens and stirs, and is warmed up to 120 ℃ the DNS acid disodium salt is fully dissolved;
(2) catalyzer is added in the catalytic hydrogenation reaction device, add the water of reactor volume 15%, after being replaced into nitrogen atmosphere in the reactor, feed hydrogen, keep pressure 0.5-3.0Mp;
(3) open hydrogenator and stir, be warming up to 250-300 ℃, the DNS acid disodium salt solution in the dissolution kettle was squeezed in the hydrogenator continuously with the time of 1-2h reacted, after charging finishes, continue to keep above-mentioned reaction conditions 20min;
(4) react the process filter that finishes and filter out catalyzer, reclaim to give over to and applies mechanically, material enters in the acid out still;
(5) open the acid out still and stir, the adding mass concentration is 50% sulphuric acid soln, and acid out to pH value is 1-2, obtains DSD acid suspension liquid;
(6) DSD acid suspension liquid is squeezed into the plate-and-frame filter press press filtration behind the acid out, gets finished product DSD acid.
2. a kind of high temperature hydrogenation reducing DNS acid disodium salt as claimed in claim 1 prepares the method for DSD acid, it is characterized in that described DNS acid disodium salt mass concentration is 50-60%.
3. a kind of high temperature hydrogenation reducing DNS acid disodium salt as claimed in claim 1 prepares the method for DSD acid, it is characterized in that described reaction pressure is 0.8-1.8Mpa.
4. a kind of high temperature hydrogenation reducing DNS acid disodium salt as claimed in claim 1 prepares the method for DSD acid, it is characterized in that described temperature of reaction is 260-280 ℃.
5. a kind of high temperature hydrogenation reducing DNS acid disodium salt as claimed in claim 1 prepares the method for DSD acid, and the add-on that it is characterized in that described catalyzer is the 0.5-5% of DNS acid disodium salt quality.
6. a kind of high temperature hydrogenation reducing DNS acid disodium salt as claimed in claim 1 prepares the method for DSD acid, it is characterized in that described catalyzer is palladium carbon, platinum carbon or ruthenium carbon.
7. a kind of high temperature hydrogenation reducing DNS acid disodium salt as claimed in claim 8 prepares the method for DSD acid, it is characterized in that the metal quality mark is 0.5-10% in the described catalyzer.
8. a kind of high temperature hydrogenation reducing DNS acid disodium salt as claimed in claim 9 prepares the method for DSD acid, it is characterized in that the metal quality mark is 1-3% in the described catalyzer.
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| CN201110096699.2A CN102206175B (en) | 2011-04-18 | 2011-04-18 | Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature |
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| CN201110096699.2A CN102206175B (en) | 2011-04-18 | 2011-04-18 | Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500395A (en) * | 2011-10-31 | 2012-06-20 | 天津大学 | TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application |
| CN106117089A (en) * | 2016-06-22 | 2016-11-16 | 康纳新型材料(杭州)有限公司 | A kind of preparation method of 4,4 ' diaminobenzil disulfonic acid |
| CN108727858A (en) * | 2018-06-07 | 2018-11-02 | 连云港莱亚化学有限公司 | A method of the oxidized waste water generated using production DSD acid prepares direct yellow dye |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL144803B1 (en) * | 1986-03-03 | 1988-07-30 | Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid | |
| JPH04321661A (en) * | 1991-04-19 | 1992-11-11 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostylbene-2,2'-disulfonic acid or salt thereof |
| JPH0680622A (en) * | 1992-09-03 | 1994-03-22 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salt |
| JPH06172295A (en) * | 1992-05-13 | 1994-06-21 | Nippon Kayaku Co Ltd | Production of 4,4'-diaminostilbene-2,2'-disulfonic acid or its salt |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500395A (en) * | 2011-10-31 | 2012-06-20 | 天津大学 | TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application |
| CN106117089A (en) * | 2016-06-22 | 2016-11-16 | 康纳新型材料(杭州)有限公司 | A kind of preparation method of 4,4 ' diaminobenzil disulfonic acid |
| CN108727858A (en) * | 2018-06-07 | 2018-11-02 | 连云港莱亚化学有限公司 | A method of the oxidized waste water generated using production DSD acid prepares direct yellow dye |
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